H2O2/[CnMIm]HCO3对CEES的消毒动力学及机理

doi:10.7503/cjcu20160487

摘要/Abstract

摘要：

合成了4种不同烷基链长的1-烷基-3-甲基咪唑碳酸氢盐([C_nMIm]HCO₃, n=2, 4, 6, 8)离子液体(ILs), 并以H₂O₂水溶液(质量分数30%)为氧化剂, 研究了H₂O₂在[C_nMIm]HCO₃离子液体、 H₂O和C₂H₅OH中对芥子气模拟剂2-氯乙基乙基硫醚(CEES)的消毒能力, 考察了离子液体烷基链长、 H₂O₂/CEES摩尔比和反应温度对消毒率的影响, 并对反应活化能和产物进行了分析. 结果表明, H₂O₂在不同溶剂中对CEES的消毒能力依次为[BMIm]HCO₃>[EMIm]HCO₃>[HMIm]HCO₃>[OMIm]HCO₃>C₂H₅OH>H₂O. 对于CEES在[BMIm]HCO₃中形成的20 mg/mL的毒剂溶液, 当n(H₂O₂)∶n(CEES)=10时, H₂O₂可在30 min内消毒99.58%的CEES, 且该体系具有一定的低温(243 K)消毒能力. 该反应为一级反应, 活化能为15.59 kJ/mol, 低于单一过碳酸钠与CEES的反应活化能. 化学发光测试结果表明, 在碳酸氢根活化过氧化氢(BAP)体系中, 咪唑基离子液体可抑制亚砜被超氧阴离子(·O^-₂)过度氧化为砜.

关键词: 离子液体, 洗消, 2-氯乙基乙基硫醚, 碳酸氢根活化过氧化氢

Abstract:

A series of environmentally benign 1-n-alkyl-3-methylimidazolium bicarbonate ionic liquids(ILs)([C_nMIm]HCO₃, n=2, 4, 6, 8) was synthesized and hydrogen peroxide was employed in decontamination against 2-chloroethyl ethyl sulfide(CEES, a mustard agent simulant) in these ILs. The influencing factors such as ILs alkyl chain length, oxidant/CEES molar ratio and temperature were tested and the activation energy, reaction product in H₂O₂/[BMIm]HCO₃ was analyzed. The results indicated that the solvents species can affect decontamination efficacy against CEES and they were in the following sequences: [BMIm]HCO₃>[EMIm]HCO₃>[HMIm]HCO₃>[OMIm]HCO₃>C₂H₅OH> H₂O. In H₂O₂/[BMIm]HCO₃ system, 99.58% of the CEES was oxidized mainly to corresponding sulfoxide after 30 min at the concentration of 20 mg/mL and O/S molar ratio of 10. The apparent activation energy of CEES oxidized by H₂O₂/[BMIm]HCO₃ was 15.59 kJ/mol. Moreover, the superoxide radical anion(·O^-₂) could be produced and oxidized ILs to 2-imidazolone, which inhibited the formation of corrosive sulfone. The result indicated that H₂O₂/[BMIm]HCO₃ system may be a new option for decontamination against CEES.

Key words: Ionic liquid, Decontamination, 2-Chloroethyl ethyl sulfide, Bicarbonate activation of H2O2

中图分类号:

O643.11

TrendMD:

王志成, 习海玲, 孔令策, 赵三平, 左言军. H₂O₂/[C_nMIm]HCO₃对CEES的消毒动力学及机理. 高等学校化学学报, 2016, 37(12): 2191.

WANG Zhicheng, XI Hailing, KONG Lingce, ZHAO Sanping, ZUO Yanjun. Kinetics and Mechanism of Decontamination Reaction of CEES in H₂O₂/[C_nMIm]HCO₃^†. Chem. J. Chinese Universities, 2016, 37(12): 2191.

图/表 10

Scheme 1 Synthetic routes of [CnMIm]HCO3(n=2, 4, 6, 8)

Table 1 1H NMR and 13C NMR data of compounds [CnMIm]HCO3(n=2, 4, 6, 8)

IL	¹H NMR (600 MHz, CDCl₃), δ	¹³C NMR (600 MHz, CDCl₃), δ
[EMIm]HCO₃	1.61(t, 3H), 3.74(s, 3H), 4.43—4.44(m, 2H), 7.73—7.74(d, 2H), 10.13(s, 1H)	16.18, 37.12, 45.65, 122.61, 124.26, 137.08
[BMIm]HCO₃	0.86(t, 3H), 1.38(m, 2H), 1.89—1.91(m, 2H), 3.91(s, 3H), 4.22(t, 2H), 7.59(s, 1H), 7.70(s, 1H), 10.05(s, 1H)	13.99, 19.95, 32.66, 37.28, 50.30, 122.78, 124.38, 137.48
[HMIm]HCO₃	0.87(t, 3H), 1.30—1.31(m, 6H), 1.91(m, 2H), 3.84(s, 3H), 4.32 (t, 2H), 7.54 (s, 1H), 7.69 (s, 1H), 9.88 (s, 1H)	14.42, 22.84, 26.33, 30.69, 31.55, 37.22, 50.54, 122.69, 124.41, 137.29
[OMIm]HCO₃	0.87(t, 3H), 1.25—1.33(m, 8H), 1.90—1.91(m, 2H), 3.85(s, 3H), 4.32(t, 2H), 7.50(s, 1H), 7.67(s, 1H), 10.03(s, 1H)	14.61, 23.11, 28.79, 29.50, 29.58, 30.85, 32.21, 37.35, 50.67, 122.62, 124.42, 137.58

Fig.1 Decontamination efficacy of CEES by H2O2 in different solventsa. [EMIm]HCO3; b. [BMIm]HCO3; c. [HMIm]HCO3; d. [OMIm]HCO3; e. [BMIm]DCA; f. [BMIm]NTf2; g. C2H5OH; h. H2O. Experimental conditions: m(CEES)=10 mg, solvents 420 μL, 30% H2O2 aqueous solution 80 μL, n(oxidant)∶n(CEES)=10, 30 min.

Fig.2 Decontamination efficacy of CEES using H2O2/[BMIm]HCO3 at different temperaturesExperimental conditions: c(CEES)=20 mg/mL,n(oxidant)∶n(CEES)=10, 30 min. Temperature/K:a. 243; b. 253; c. 273; d. 298; e. 313.

Fig.3 Apparent activation energy of oxidation of CEES

Fig.4 GC-MS spectrum of CEES oxidation products in H2O2/[BMIm]HCO3

Fig.5 Oxidation products of CEES in H2O2/[BMIm]HCO3

Fig.6 CL kinetics of H2O2 in lucigenin solution which containing basic ILsa. [BMIm]HCO3; b. [BMIm]DCA; c. [BMIm]NTf2.Experimental conditions: 2 mL lucigenin, 100 μL H2O2, 50 μL ILs.

Fig.7 Formation dynamics of ·O2- in H2O2/[BMIm]HCO3Curves a—g were the FTIR spectrum of H2O2/[BMIm]HCO3 mixture at 1, 2, 5, 10, 15, 20, 30 min, respectively.Inset: the growth trend of ·O2- was fitted bo a logarithmic function.

Scheme 2 Possible reaction mechanism between CEES with H2O2/[BMIm]HCO3

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H₂O₂/[C_nMIm]HCO₃对CEES的消毒动力学及机理

Kinetics and Mechanism of Decontamination Reaction of CEES in H₂O₂/[C_nMIm]HCO₃^†

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